Aggregating reagents and methods for making and using same

ABSTRACT

Methods including using fluid including an aggregating composition including heterocyclic aromatic amines, substituted heterocyclic aromatic amines, polyvinyl heterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromatic amine and non amine polymerizable monomers (ethylenically unsaturated mononers and diene monomers), or mixtures or combinations thereof in the absence of phosphate esters or amine-phosphate reaction products during drilling or fracturing operations to alter self-aggregating properties and/or aggregation propensities of the particles, surfaces, and/or materials in or entrained in the fluid.

RELATED APPLICATIONS

This application is continuation of U.S. patent application Ser. No.13/247,985 filed 28 Sep. 2011.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the present invention relate to: (1) aggregating agentsfor treating solid materials, surfaces, and/or substrates includingmetal oxide or ceramic solid materials, surfaces, and/or substrates(natural or synthetic), metallic solid materials, surfaces, and/orsubstrates, polymeric or plastic solid materials, surfaces, and/orsubstrates (natural or synthetic), solid plant materials, surfaces,and/or substrates, or other types of solid materials, surfaces, orsubstrates, (2) treated materials and (3) methods for making and usingsame.

More particularly, embodiments of the present invention relates toaggregating agents for particulate solid materials, surfaces, and/orsubstrates, where the aggregating agents modify surface properties ofthe materials, surfaces, and/or substrates increasing their aggregatingpropensity or properties. The present invention also relates to coatedor modified materials, surfaces, or substrates, where the coatingmodifies an aggregating propensity of the materials, surfaces, orsubstrates. The present invention also relates to methods for alteringan aggregation propensity of materials, surfaces, or substratesespecially in downhole applications and in any other application, wherealtering an aggregation propensity of particulate solid materials,surfaces, or substrates is desirable or beneficial.

2. Description of the Related Art

Historically, the problem of aggregating particulate materials downholehas been addressed using epoxy resins, phenolic resins and tackifyingagents as described in U.S. Pat. Nos. 5,833,000; 5,871,049; 5,775,425;and 5,787,986.

More recently, reactions products alkyl pyridines and phosphate esterswere introduced as inner salt of alkyl pryridinium phosphate esterproducts, which resulted in a decrease in a zeta potential of thesubstrate and therefore helped agglomeration properties of the as setforth in U.S. Pat. No. 7,392,847.

Although there products are useful for aggregating or agglomeratingparticulates and treating formation surfaces to alter a zeta potentialof the surfaces and/or particles, there is still an need in the art forproducts that can augment aggregating or agglomerating properties ofparticles and/or surfaces and/or augment zeta potentials of particlesand/or surfaces.

SUMMARY OF THE INVENTION Compositions

Embodiments of the present invention provide aggregating compositionsfor treating solid particles, surfaces and/or materials, where thecompositions comprise amines including heterocyclic aromatic amines,substituted heterocyclic aromatic amines, polyvinyl heterocyclicaromatic amines, co-polymers of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof in the absence ofphosphate esters, optionally ethoxylated alcohols, and optionallyglymes, which form complete or partial coating on the particles,surfaces and/or materials altering self-aggregating properties and/oraggregation propensities of the particles, surfaces, and/or materials.

Embodiments of the present invention provide particles, surfaces, and/ormaterials including a partial or complete coating of an aggregatingcomposition of this invention, where the partial or complete coatingalters self-aggregating properties and/or aggregation propensities ofthe particles, surfaces, and/or materials.

Embodiments of the present invention provide coatings of an aggregatingcomposition comprising heterocyclic aromatic amines, substitutedheterocyclic aromatic amines, poly vinyl heterocyclic aromatic amines,co-polymers of vinyl heterocyclic aromatic amine and non aminepolymerizable monomers (ethylenically unsaturated mononers and dienemonomers), or mixtures or combinations thereof in the absence ofphosphate esters, optionally ethoxylated alcohols, and optionallyglymes, where the coatings deform under pressure and impart an enhancedaggregating propensity to the particles, surfaces and/or materials.

Embodiments of the present invention provide a structure or substratehaving surfaces partially or completed coated with an aggregatingcomposition comprise heterocyclic aromatic amines, substitutedheterocyclic aromatic amines, poly vinyl heterocyclic aromatic amines,co-polymers of vinyl heterocyclic aromatic amine and non aminepolymerizable monomers (ethylenically unsaturated mononers and dienemonomers), or mixtures or combinations thereof in the absence ofphosphate esters, optionally ethoxylated alcohols, and optionallyglymes, where the coating is deformable and where the substrate isideally suited for filtering fines and/or other particulate materialsform a fluid, especially fluids used in oil/gas well drilling,completion, production, fracturing, propping, other production enhancingprocesses or other related applications. The substrates or structurescan be ceramic or ceramic fibers or wools coated partially or completelywith the compositions of this invention. Such substrates or structuresare well suited for filter media to be used with or without screens.

Method for Treating

Embodiments of the present invention provide methods for changing oraltering an aggregation potential or propensity of a solid particles,surfaces, and/or materials, where the method includes the step ofcontacting the particles, surfaces, and/or materials with a compositioncomprising heterocyclic aromatic amines, substituted heterocyclicaromatic amines, poly vinyl heterocyclic aromatic amines, co-polymers ofvinyl heterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof in the absence of phosphate esters, optionallyethoxylated alcohols, and optionally glymes under conditions sufficientfor the composition to form partial or complete coatings on particles,surfaces, and/or materials.

Methods for Using the Treating Methods Fracturing

Embodiments of the present invention provide methods for fracturing aformation including the step of pumping a fracturing fluid including aproppant into a producing formation at a pressure sufficient to fracturethe formation and to enhance productivity, where the proppant props openthe formation after fracturing and where the proppant comprises a solidparticles treated with a treating composition comprising heterocyclicaromatic amines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, optionally ethoxylated alcohols, andoptionally glymes under conditions sufficient for the composition toform a partial or complete coating on the particles.

Embodiments of the present invention provide methods for fracturing aformation including the step of pumping a fracturing fluid including aproppant and an aggregating composition comprising heterocyclic aromaticamines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, optionally ethoxylated alcohols, andoptionally glymes into a producing formation at a pressure sufficient tofracture the formation and to enhance productivity. The compositionresults in a modification of an aggregation propensity, and/orzeta-potential of the proppant, formation particles and/or formationsurfaces so that the formation particles and/or proppant aggregateand/or cling to the formation surfaces.

Embodiments of the present invention provide methods for fracturing aformation including the step of pumping a fracturing fluid including anaggregating composition comprising heterocyclic aromatic amines,substituted heterocyclic aromatic amines, poly vinyl heterocyclicaromatic amines, co-polymers of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof in the absence ofphosphate esters, optionally ethoxylated alcohols, and optionally glymesinto a producing formation at a pressure sufficient to fracture theformation and to enhance productivity. The composition results in aaltering an aggregation propensity, potential and/or zeta-potential ofthe formation particles and/or formation surfaces so that the formationparticles aggregate and/or cling to the formation surfaces. The methodsmay also include the step of pumping a proppant comprising a uncoatedand/or coated particles after fracturing so that the particles prop openthe fracture formation and where the coated particles tend to aggregateon the formation surfaces and/or formation particles formed duringfracturing.

Drilling

Embodiments of the present invention provide methods for drillingincluding the step of while drilling, circulating a drilling fluid, toprovide bit lubrication, heat removal and cutting removal, where thedrilling fluid includes an aggregating composition comprisingheterocyclic aromatic amines, substituted heterocyclic aromatic amines,poly vinyl heterocyclic aromatic amines, co-polymers of vinylheterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof in the absence of phosphate esters, optionallyethoxylated alcohols, and optionally glymes. The compositions alters anaggregation potential or propensity and/or a zeta potential ofparticulate materials in the drilling fluid or that becomes entrained inthe drilling fluid to increase solids removal. The methods may beoperated in over-pressure conditions, under-balanced conditions or undermanaged pressure conditions. The methods are especially well tailored tounder-balanced or managed pressure conditions.

Embodiments of the present invention provide methods for drillingincluding the step of while drilling, circulating a first drilling fluidto provide bit lubrication, heat removal and cutting removal. Uponencountering an underground structure that produces undesirablequantities of particulate solids, changing the first drilling fluid to asecond drilling fluid including a composition comprising heterocyclicaromatic amines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, optionally ethoxylated alcohols, andoptionally glymes to provide bit lubrication, heat removal and cuttingremoval and to alter an aggregation potential or an absolute value of azeta potential of the particulate solids in the drilling fluid orformation or that becomes entrained in the drilling fluid to increasesolids removal and to decrease particles flowing from the formation intothe drilling fluid. The methods may be operated in over-pressureconditions or under-balanced conditions or under managed pressureconditions. The methods are especially well tailored to under-balancedor managed pressure conditions.

Embodiments of the present invention provide methods for drillingincluding the step of while drilling, circulating a first drilling fluidto provide bit lubrication, heat removal and cutting removal. Uponencountering an underground structure that produces undesirablequantities of particulate solids, changing the first drilling fluid to asecond drilling fluid including a composition comprising heterocyclicaromatic amines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, optionally ethoxylated alcohols, andoptionally glymes to provide bit lubrication, heat removal and cuttingremoval and to increase an aggregation potential or decrease in theabsolute value of the zeta potential of any particulate solids in thedrilling fluid or that becomes entrained in the drilling fluid toincrease solids removal. After passing through the structure thatproduces an undesired quantities of particulate solids, change thesecond drilling fluid to the first drilling fluid or a third drillingfluid. The methods may be operated in over-pressure conditions orunder-balanced conditions or under managed pressure conditions. Themethods are especially well tailored to under-balanced or managedpressure conditions.

Producing

Embodiments of the present invention provide methods for producingincluding the step of circulating and/or pumping a fluid into a well onproduction, where the fluid includes a composition comprisingheterocyclic aromatic amines, substituted heterocyclic aromatic amines,poly vinyl heterocyclic aromatic amines, co-polymers of vinylheterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof in the absence of phosphate esters, optionallyethoxylated alcohols, and optionally glymes, which alters an aggregationpotential or an absolute value of a zeta potential of any particulatesolids in the fluid or that becomes entrained in the fluid to increasesolid particle removal and to decrease the potential of the particles toplug the formation and/or the production tubing.

Embodiments of the present invention provide methods for controllingsand or fines migration including the step of pumping a fluid includinga composition comprising heterocyclic aromatic amines, substitutedheterocyclic aromatic amines, poly vinyl heterocyclic aromatic amines,co-polymers of vinyl heterocyclic aromatic amine and non aminepolymerizable monomers (ethylenically unsaturated mononers and dienemonomers), or mixtures or combinations thereof in the absence ofphosphate esters, optionally ethoxylated alcohols, and optionally glymesthrough a matrix at a rate and pressure into a formation to control sandand fine production or migration into the production fluids.

Embodiments of the present invention provide other methods forcontrolling sand or fines migration including the step of depositing acoated particulate solid material of this invention adjacent screen-typesand and fines control devices so that the sand and/or fines areattracted to the coated particles and do not encounter or foul thescreen of the screen-type device.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have found that aggregating compositions can be preparedthat alter an aggregation propensity, aggregation potential and/or azeta potential of solid particles, surfaces, and/or materials, when theparticles, surfaces and/or materials are treated with an amount of thecompositions sufficient to form partial or complete coating on theparticles, surfaces, and/or materials. The inventors have also foundthat particles, surfaces, and/or materials may be treated with thecompositions of this invention, where the particles, surfaces and/ormaterials are coated partially or completely with the composition toform modified or coated particles, surfaces, and/or materials. Theresulting modified or coated particles, surfaces and/or materials haveimproved aggregation tendencies and/or propensities and/or alteredparticle zeta potentials. The inventors have also found that thecompositions, the modified metal-oxide-containing particles, surfacesand/or materials may be used in oil field applications includingdrilling, fracturing, producing, injecting, sand control, or any otherdownhold application. The inventors have also found that the modifiedparticulate metal-oxide-containing solid particles or particles of anyother solid material may be used in any other application, whereincreased particle aggregation potentials are desirable or wheredecreased absolute values of the zeta potential of the particles, whichis a measure of aggregation propensity. The inventors have also foundthat a coated particulate metal-oxide-containing solid compositions maybe formed, where the coating is deformable and the coated particles tendto self-aggregate and tend to cling to surfaces having similar coatingsor having similar chemical and/or physical properties to that of thecoating. That is to say, the coated particles tend to prefer likecompositions, which increases their self-aggregation propensity andincreases their ability to adhere to surface that have similar chemicaland/or physical properties. The inventors have found that the coatingcompositions of this invention are distinct from known compositions formodifying particle aggregation propensities and that the coatedparticles are ideally suited as proppants, where the particles havealtered zeta potentials that change the charge on the particles causingthem to attract and agglomerate. The change in zeta potential oraggregation propensity causes each particle to have an increasedfrictional drag keeping the proppant in the fracture. The compositionsare also ideally suited for decreasing fines migrating into a fracturepack or to decrease the adverse impact of fines migration into afractured pack. What is very surprising and unexpected about the presentcompositions is that the coating are formed in the absence of phosphateesters. In the prior applications cited above, the coating that wereformed required a reaction produce between an amine and a phosphateester. The fact that compositions comprising heterocyclic aromaticamines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof wouldbe able to modify the aggregating propensity of surface and particlestreated with the composition.

In the case of drilling, the compositions of this invention may be usedto coat the formation and formation cuttings during drilling, becausethe particle tend to self aggregate and/or cling to similarly modifiedparticles and/or formation surfaces. Again, an advantage of theself-aggregation is a reduced tendency of the cuttings to foul or plugscreens. Additional advantages are to coat the formation walls with acomposition of this invention during drilling to consolidate theformation and to consolidate or aggregate fines or particles in thedrilling fluid to keep the rheological properties of the drilling fluidfrom changing and increasing equivalent circulating density (ECD).

One problem in oil and gas production from wells is the control of theco-production of fines and sand from producing formations. Besides theco-production of particulate materials during oil and/or gas productionfrom wells, flowback of proppant and/or fines after formation fracturingis also a problem. Additionally, it has been found that Steam AssistedGravity Drainage (SAGD) processing of oil and/or gas wells de-stabilizessand/fines during and after steam injection during SAGD processing.

Certain embodiments of this invention relate to aggregating compositionscomprising heterocyclic aromatic amines, substituted heterocyclicaromatic amines, poly vinyl heterocyclic aromatic amines, co-polymers ofvinyl heterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof in the absence of phosphate esters, optionallyethoxylated alcohols, and optionally glymes.

Basically the difference of this system compared to the previouslypatented system cited above is that this new systems are not reactionproducts of heterocyclic aromatic amines, substituted heterocyclicaromatic amines, poly vinyl heterocyclic aromatic amines, co-polymers ofvinyl heterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof with a phosphate ester. Thus, the presentaggregating compositions are basically high molecular weightheterocyclic aromatic amines, substituted heterocyclic aromatic amines,poly vinyl heterocyclic aromatic amines, co-polymers of vinylheterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof in a carrier. The compositions may also includeethoxylated alcohols, and glymes

Compositions

Embodiments of the present invention broadly relate to compositionsincluding aggregating systems including one or a plurality of arylamines (heterocyclic aromatic amines), one or a plurality of substitutedaryl amines (substituted heterocyclic aromatic amines), one or aplurality of polymers or copolymers including at least one monomer vinylaryl amine (vinyl heterocyclic aromatic amine), and/or mixtures orcombinations thereof. In certain embodiments, the compositions of thisinvention include high molecular weight one or a plurality of arylamines (heterocyclic aromatic amines), one or a plurality of substitutedaryl amines (substituted heterocyclic aromatic amines), one or aplurality of polymers or copolymers including at least one monomer vinylaryl amine (vinyl heterocyclic aromatic amine), and/or mixtures orcombinations thereof in a carrier, in the absence of phosphate esters.The compositions may also include ethoxylated alcohols, and glymes. Thecompositions modify surfaces of solid materials or portions thereofaltering the chemical and/or physical properties of the surfaces. Thealtered properties permit the surfaces to become self attracting or topermit the surfaces to be attractive to material having similar chemicaland/or physical properties. In the case of particles including metaloxide particles such as particles of silica, alumina, titania, magnesia,zirconia, other metal oxides or oxides including a mixture of thesemetal oxides (natural or synthetic), the composition forms a complete orpartial coating on the surfaces of the particles. The coating caninteract with the surface by chemical and/or physical interactionsincluding, without limitation, chemical bonds, hydrogen bonds,electrostatic interactions, dipolar interactions, hyperpolarizabilityinteractions, cohesion, adhesion, adherence, mechanical adhesion or anyother chemical and/or physical interaction that allows a coating to formon the particles. The coated particles have a greater aggregation oragglomeration propensity than the uncoated particles. Thus, theparticles before treatment may be free flowing, while after coating arenot free flowing, but tend to clump, aggregate and/or agglomerate. Incases, where the composition is used to coat surfaces of a geologicalformation, a synthetic metal oxide structure and/or metal-oxidecontaining particles, the particles will not only tend to aggregatetogether, the particles also will tend to cling to the coated formationor structural surfaces.

Treated Structures and Substrates

Embodiments of the present invention also broadly relate to structuresand substrates treated with a composition comprising heterocyclicaromatic amines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, where the structures and substrates includesurfaces that are partially or completely coated with a composition ofthis invention. The compositions may also include ethoxylated alcohols,and glymes. The structures or substrates can be ceramic or metallic orfibrous. The structures or substrates can be spun such as a glass woolor steel wool or can be honeycombed like catalytic converters or thelike that include channels that force fluid to flow through torturedpaths so that particles in the fluid are forced in contact with thesubstrate or structured surfaces. Such structures or substrates areideally suited as particulate filters or sand control media.

Methods for Treating Particulate Solids

Embodiments of the present invention broadly relate to methods fortreating metal oxide-containing surfaces including the step ofcontacting the metal oxide-containing surface with a compositioncomprising heterocyclic aromatic amines, substituted heterocyclicaromatic amines, poly vinyl heterocyclic aromatic amines, co-polymers ofvinyl heterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof in the absence of phosphate esters. Thecompositions may also include ethoxylated alcohols, and glymes. Thecompositions are thought to form a coating on the surface altering theproperties of the surface so that the surface is now capable tointeracting with similarly treated surfaces to form agglomerated and/oraggregated structures. The treating may be designed to coat continuousmetal oxide containing surfaces and/or the surfaces of metal oxidecontaining particles. If both are treated, then the particles cannotonly self-aggregate, but the particles can also aggregate, agglomerateand/or cling to the coated continuous surfaces. The compositions can beused in fracturing fluids, in drilling fluids, in completion fluids, insand control applications or any other downhole application.Additionally, the coated particles can be used in fracturing fluids.Moreover, structures, screens or filters coated with the compositions ofthis invention can be used to attract and remove fines that have beenmodified with the compositions of this invention.

Method for Fracturing and/or Propping

Embodiments of the present invention broadly relate to methods forfracturing a formation including the step of pumping a fracturing fluidincluding a composition comprising heterocyclic aromatic amines,substituted heterocyclic aromatic amines, poly vinyl heterocyclicaromatic amines, co-polymers of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof in the absence ofphosphate esters into a producing formation at a pressure sufficient tofracture the formation. The compositions may also include ethoxylatedalcohols, and glymes. The composition modifies an aggregation potentialand/or zeta-potential of formation particles and formation surfacesduring fracturing so that the formation particles aggregate and/or clingto the formation surfaces or each other increasing fracturing efficiencyand increasing productivity of the fracture formation. The compositionof this invention may also be used in a pre-pad step to modify thesurfaces of the formation so that during fracturing the formationsurfaces are pre-coated. The pre-pad step involves pumping a fluid intothe formation ahead of the treatment to initiate the fracture and toexpose the formation face with fluids designed to protect the formation.Beside just using the composition as part of the fracturing fluid, thefracturing fluid can also include particles that have been prior treatedwith the composition of this invention, where the treated particles actas proppants to prop open the formation after fracturing. If thefracturing fluid also includes the composition, then the coated particleproppant will adhere to formation surfaces to a greater degree thanwould uncoated particle proppant.

In an alternate embodiment of this invention, the fracturing fluidincludes particles coated with a composition comprising heterocyclicaromatic amines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters as proppant. The compositions may alsoinclude ethoxylated alcohols, and glymes. In this embodiment, theparticles have a greater self-aggregation propensity and will tend toaggregate in locations that may most need to be propped open. In allfracturing applications including proppants coated with or that becomecoated with the composition of this invention during fracturing, thecoated proppants are likely to have improved formation penetration andadherence properties. These greater penetration and adherence oradhesion properties are due not only to a difference in the surfacechemistry of the particles relative to the surface chemistry ofun-treated particles, but also due to a deformability of the coatingitself. Thus, the inventors believe that as the particles are beingforced into the formation, the coating will deform to allow theparticles to penetrate into a position and as the pressure is removedthe particles will tend to remain in place due to the coatinginteraction with the surface and due to the relaxation of the deformedcoating. In addition, the inventors believe that the altered aggregationpropensity of the particles will increase proppant particle density inregions of the formation most susceptible to proppant penetrationresulting in an enhance degree of formation propping.

Method for Drilling

Embodiments of the present invention also broadly relate to methods fordrilling including the step of, while drilling, circulating a drillingfluid to provide bit lubrication, heat removal and cutting removal,where the drill fluid includes a composition comprising heterocyclicaromatic amines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, which increases an aggregation potential ordecrease an absolute value of the zeta potential of any particulatesolids in the drilling fluid or that becomes entrained in the drillingfluid to increase solids removal. The compositions may also includeethoxylated alcohols, and glymes.

Embodiments of the present invention also broadly relate to methods fordrilling including the step of while drilling, circulating a firstdrilling fluid to provide bit lubrication, heat removal and cuttingremoval. Upon encountering an underground structure that producesundesirable quantities of particulate solids including metaloxide-containing solids, changing the first drilling fluid for a seconddrilling fluid including a composition comprising heterocyclic aromaticamines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters to provide bit lubrication, heat removal andcutting removal and to increase an aggregation potential or decrease anabsolute value of the zeta potential of any solid including particulatemetal oxide-containing solids in the drilling fluid or that becomesentrained in the drilling fluid to increase solids removal. Thecompositions may also include ethoxylated alcohols, and glymes.

Embodiments of the present invention also broadly relate to methods fordrilling including the step of, while drilling, circulating a firstdrilling fluid to provide bit lubrication, heat removal and cuttingremoval. Upon encountering an underground structure that producesundesirable quantities of particulate solids including metaloxide-containing solids, changing the first drilling fluid for a seconddrilling fluid including a composition comprising heterocyclic aromaticamines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters to provide bit lubrication, heat removal andcutting removal and to increase an aggregation potential or zetapotential of any particulate solid including metal oxide-containingsolid in the drilling fluid or that becomes entrained in the drillingfluid to increase solids removal. After passing through the structurethat produces an undesired quantities of particulate metaloxide-containing solids, change the second drilling fluid for the firstdrilling fluid or a third drilling fluid. The compositions may alsoinclude ethoxylated alcohols, and glymes.

Method for Producing

Embodiments of the present invention also broadly relate to methods forproducing including the step of circulating and/or pumping a fluid into,where the fluid includes a composition comprising heterocyclic aromaticamines, substituted heterocyclic aromatic amines, poly vinylheterocyclic aromatic amines, co-polymers of vinyl heterocyclic aromaticamine and non amine polymerizable monomers (ethylenically unsaturatedmononers and diene monomers), or mixtures or combinations thereof in theabsence of phosphate esters, which increases an aggregation potential ordecreases an absolute value of the zeta potential of any particulatesolid including a metal oxide-containing solid in the fluid or thatbecomes entrained in the fluid to increase solids removal and todecrease the potential of the particles plugging the formation and/orproduction tubing. The compositions may also include ethoxylatedalcohols, and glymes.

Suitable Materials for Use in the Invention

Suitable amines capable of forming a deformable coating on a solidparticles, surfaces, and/or materials include, without limitation,heterocyclic aromatic amines, substituted heterocyclic aromatic amines,poly vinyl heterocyclic aromatic amines, co-polymers of vinylheterocyclic aromatic amine and non amine polymerizable monomers(ethylenically unsaturated mononers and diene monomers), or mixtures orcombinations thereof, where the substituents of the substitutedheterocyclic aromatic amines are carbyl groups having between aboutbetween about 1 and 40 carbon atoms and the required hydrogen atoms tosatisfy the valence and where one or more of the carbon atoms can bereplaced by one or more hetero atoms selected from the group consistingof boron, nitrogen, oxygen, phosphorus, sulfur or mixture orcombinations thereof and where one or more of the hydrogen atoms can bereplaced by one or more single valence atoms selected from the groupconsisting of fluorine, chlorine, bromine, iodine or mixtures orcombinations thereof. In certain embodiments, amines suitable for use inthis invention include, without limitation, aniline and alkyl anilinesor mixtures of alkyl anilines, pyridines and alkyl pyridines or mixturesof alkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkylpyrroles, piperidine and alkyl piperidines or mixtures of alkylpiperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkylpyrrolidines, indole and alkyl indoles or mixture of alkyl indoles,imidazole and alkyl imidazole or mixtures of alkyl imidazole, quinolineand alkyl quinoline or mixture of alkyl quinoline, isoquinoline andalkyl isoquinoline or mixture of alkyl isoquinoline, pyrazine and alkylpyrazine or mixture of alkyl pyrazine, quinoxaline and alkyl quinoxalineor mixture of alkyl quinoxaline, acridine and alkyl acridine or mixtureof alkyl acridine, pyrimidine and alkyl pyrimidine or mixture of alkylpyrimidine, quinazoline and alkyl quinazoline or mixture of alkylquinazoline, or mixtures or combinations thereof. In certainembodiments, the poly vinyl heterocyclic amines include, withoutlimitation, polymers and copolymers of vinyl pyridine, vinyl substitutedpyridine, vinyl pyrrole, vinyl substituted pyrroles, vinyl piperidine,vinyl substituted piperidines, vinyl pyrrolidine, vinyl substitutedpyrrolidines, vinyl indole, vinyl substituted indoles, vinyl imidazole,vinyl substituted imidazole, vinyl quinoline, vinyl substitutedquinoline, vinyl isoquinoline, vinyl substituted isoquinoline, vinylpyrazine, vinyl substituted pyrazine, vinyl quinoxaline, vinylsubstituted quinoxaline, vinyl acridine, vinyl substituted acridine,vinyl pyrimidine, vinyl substituted pyrimidine, vinyl quinazoline, vinylsubstituted quinazoline, or mixtures and combinations thereof. Incertain embodiments, the heterocyclic aromatic amines comprise HAP™-310available from Vertellus Specialties Inc.

Suitable glymes including, without limitation, diethylene glycoldimethyl ether, ethylene, propylene glycol dimethyl ether, dipropyleneglycol dimethyl ether, diethylene glycol diethyl ether, ethylene,propylene glycol diethyl ether, dipropylene glycol diethyl ether, ormixture or combinations thereof. In certain embodiments, the glyme isdipropylene glycol dimethyl ether sold as Proglyme from NovolyteTechnologies of Independence, Ohio.

Suitable carriers for use in the present invention include, withoutlimitation, low molecular weight alcohols having between 1 and 5 carbonatoms, where one or more of the carbon atoms may be oxygen or mixturesor combinations thereof. Exemplary examples include methanol, ethanol,propanaol, isopropyl alcohol, butanol, isobutanol, pentanol,isopentanol, neopentanol or mixture or combinations thereof.

Suitable ethoxylated alcohols include, without limitation, anyethoxylated alcohol having an HLB value between about 6 and 10 ormixtures or combinations thereof. In other, embodiments, the ethoxylatedalcohol having an HLB value between about 7 and 9 or mixtures orcombinations thereof. In other embodiments, ethoxylated alcohol havingan HLB value between about 7.5 and 8.5 or mixtures or combinationsthereof. In other embodiments, ethoxylated alcohol having an HLB valuebetween about 8 or mixtures or combinations thereof. Exemplaryethoxylated alcohols include, without limitation, C₁₂-C₁₈ alcohols,linear or branched, and 2 to 6 ethoxylations (2 to 6 ethyleneoxideunits) per alcohol or mixtures or combinations thereof. In certainembodiments, the ethoxylated alcohols include C₁₂-C₁₄ alcohols, linearor branched with 2 to 5 ethoxylations (2 to 5 ethyleneoxide units) peralcohol or mixtures or combinations thereof. In certain embodiments, theethoxylated alcohols include C₁₂ alcohols, linear or branched with 2 to5 ethoxylations (2 to 5 ethyleneoxide units) per alcohol or mixtures orcombinations thereof. In certain embodiments, the ethoxylated alcoholsinclude C₁₃ alcohols, linear or branched with 2 to 5 ethoxylations (2 to5 ethyleneoxide units) per alcohol. In certain embodiments, theethoxylated alcohols include C₁₄ alcohols, linear or branched with 2 to5 ethoxylations (2 to ethyleneoxide units) per alcohol or mixtures orcombinations thereof. In certain embodiments, the ethoxylated alcohol isan ethoxylated iso-tridecyl alcohol such as ALFONIC® TDA-3 available forSasol North Americas, Inc.

Suitable solid materials suitable for being coated with the compositionsof this invention include, without limitation, metal oxides and/orceramics, natural or synthetic, metals, plastics and/or other polymericsolids, solid materials derived from plants, or any other solid materialthat does or may find use in downhole applications or mixtures orcombinations thereof. Metal oxides including any solid oxide of ametallic element of the periodic table of elements. Exemplary examplesof metal oxides and ceramics include actinium oxides, aluminum oxides,antimony oxides, boron oxides, barium oxides, bismuth oxides, calciumoxides, cerium oxides, cobalt oxides, chromium oxides, cesium oxides,copper oxides, dysprosium oxides, erbium oxides, europium oxides,gallium oxides, germanium oxides, iridium oxides, iron oxides, lanthanumoxides, lithium oxides, magnesium oxides, manganese oxides, molybdenumoxides, niobium oxides, neodymium oxides, nickel oxides, osmium oxides,palladium oxides, potassium oxides, promethium oxides, praseodymiumoxides, platinum oxides, rubidium oxides, rhenium oxides, rhodiumoxides, ruthenium oxides, scandium oxides, selenium oxides, siliconoxides, samarium oxides, silver oxides, sodium oxides, strontium oxides,tantalum oxides, terbium oxides, tellurium oxides, thorium oxides, tinoxides, titanium oxides, thallium oxides, thulium oxides, vanadiumoxides, tungsten oxides, yttrium oxides, ytterbium oxides, zinc oxides,zirconium oxides, ceramic structures prepared from one or more of theseoxides and mixed metal oxides including two or more of the above listedmetal oxides. Exemplary examples of plant materials include, withoutlimitation, shells of seed bearing plants such as walnut shells, pecanshells, peanut shells, shells for other hard shelled seed formingplants, ground wood or other fibrous cellulosic materials, or mixturesor combinations thereof.

Compositional Ranges and Properties

Embodiments of the aggregating compositions of this invention including:

from about 50 wt. % to about 80 wt. % of a heterocyclic aromatic amine,a substituted heterocyclic aromatic amine, poly vinyl heterocyclicaromatic amine, a co-polymer of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof;

from about 10 wt. % to about 30 wt. % of a carrier,

from about 0 wt % to about 30 wt. % of a glyme, and

from about 0 wt. % to about 10 wt. % of an ethoxylated alcohol having anHLB value between about 6 and about 10.

In other embodiments of the aggregating compositions of this inventionincluding:

from about 50 wt. % to about 80 wt. % of a heterocyclic aromatic amine,a substituted heterocyclic aromatic amine, poly vinyl heterocyclicaromatic amine, a co-polymer of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof;

from about 10 wt. % to about 25 wt. % of a carrier,

from about 0 wt % to about 25 wt. % of a glyme, and

from about 0 wt. % to about 10 wt. % of an ethoxylated alcohol having anHLB value between about 6 and about 10.

In other embodiments of the aggregating compositions of this inventionincluding:

from about 50 wt. % to about 80 wt. % of a heterocyclic aromatic amine,a substituted heterocyclic aromatic amine, poly vinyl heterocyclicaromatic amine, a co-polymer of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof;

from about 10 wt. % to about 25 wt. % of a carrier,

from about 1 wt % to about 25 wt. % of a glyme, and

from about 0.5 wt. % to about 10 wt. % of an ethoxylated alcohol havingan HLB value between about 6 and about 10.

In other embodiments of the aggregating compositions of this inventionincluding:

from about 50 wt. % to about 80 wt. % of a heterocyclic aromatic amine,a substituted heterocyclic aromatic amine, poly vinyl heterocyclicaromatic amine, a co-polymer of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof;

from about 10 wt. % to about 25 wt. % of a carrier,

from about 2 wt % to about 25 wt. % of a glyme, and

from about 1 wt. % to about 10 wt. % of an ethoxylated alcohol having anHLB value between about 6 and about 10.

In other embodiments of the aggregating compositions of this inventionincluding:

from about 50 wt. % to about 80 wt. % of a heterocyclic aromatic amine,a substituted heterocyclic aromatic amine, poly vinyl heterocyclicaromatic amine, a co-polymer of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof;

from about 10 wt. % to about 25 wt. % of a carrier,

from about 5 wt % to about 25 wt. % of a glyme, and

from about 1 wt. % to about 9 wt. % of an ethoxylated alcohol having anHLB value between about 6 and about 10.

In other embodiments of the aggregating compositions of this inventionincluding:

from about 50 wt. % to about 80 wt. % of a heterocyclic aromatic amine,a substituted heterocyclic aromatic amine, poly vinyl heterocyclicaromatic amine, a co-polymer of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers (ethylenically unsaturated mononers anddiene monomers), or mixtures or combinations thereof;

from about 10 wt. % to about 25 wt. % of a carrier,

from about 5 wt % to about 25 wt. % of a glyme, and

from about 1 wt. % to about 8 wt. % of an ethoxylated alcohol having anHLB value between about 6 and about 10.

Embodiments of the aggregating compositions of this invention may alsobe tailored to have a specific agglomerating effect on particulatematerial such as sand. By varying the about of the ethoxylated alcoholcomponent, the agglomerating effect may be tuned from good, to averageto poor. This tailoring ability may be adjusted on the fly, simply bychanging the relative amount of the ethoxylated alcohol component in theaggregating composition. For compositions having good agglomeratingproperties, the ethoxylated alcohol contents ranges from 0 wt. % toabout 4 wt. %. For compositions having average agglomerating properties,the ethoxylated alcohol contents ranges from 5 wt. % to about 7 wt. %.For compositions having poor agglomerating properties, the ethoxylatedalcohol contents is greater than 7 wt. % and generally, between about 8wt. % to about 15 wt. %.

EXPERIMENTS OF THE INVENTION Example 1

Tests Replacing MeOG and EG from the formulations

Formula 1 Formula 3 Formula 5 Formula 6 23% Methanol 23% IPA 20% IPA 20%IPA 77% HAP-310 23% Proglyme 23% Proglyme 16% Proglyme 54% HAP-310  3%TDA-3 10% TDA-3 54% HAP-310 54% HAP-310 ALFONIC ® TDA-3 Ethoxylate -Isotridecanol, ethoxylated, available from Sasol North America Inc. ofHouston, TX 77079 Proglyme C₈H₁₈O₃ available from Novolyte Technologies,Inc. of Cleveland, Ohio HAP ™-310 available from Vertellus SpecialtiesInc.

Formula Agglomeration HAP:Proglyme (50:50) & 1% TDA-3 Good HAP:Proglyme(50:50) & 6% TDA-3 Average HAP:Proglyme (50:50) & 10% TDA-3 PoorHAP:Proglyme (50:50) & 15% TDA-3 Poor SandAid & 0.5% TDA-3 Good SandAid& 1.0% TDA-3 Good SandAid & 2.0% TDA-3 Good SandAid & 3.0% TDA-3 GoodSandAid & 4.0% TDA-3 Good SandAid & 6.0% TDA-3 Average SandAid & 10%TDA-3 Poor

All references cited herein are incorporated by reference. Although theinvention has been disclosed with reference to its preferredembodiments, from reading this description those of skill in the art mayappreciate changes and modification that may be made which do not departfrom the scope and spirit of the invention as described above andclaimed hereafter.

We claim:
 1. A method for drilling comprising the step of: whiledrilling, circulating a drilling fluid, to provide bit lubrication, heatremoval and cutting removal, where the drilling fluid includes anaggregating composition comprising heterocyclic aromatic amines,substituted heterocyclic aromatic amines, polyvinyl heterocyclicaromatic amines, co-polymers of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers, or mixtures and combinations thereofin the absence of phosphate esters and amine-phosphate ester reactionproducts, and where the aggregating composition alters an aggregationpotential or propensity and/or a zeta potential of particulate materialsin the drilling fluid or that becomes entrained in the drilling fluid toincrease solids removal.
 2. The method of claim 1, wherein drillingconditions comprise over-pressure drilling conditions, under-balanceddrilling conditions, or under managed pressure drilling conditions. 3.The method of claim 2, wherein the drilling conditions areunder-balanced drilling conditions.
 4. The method of claim 2, whereinthe drilling conditions are managed pressure drilling conditions.
 5. Themethod of claim 1, wherein the aggregating composition further comprisesethoxylated alcohols, or glymes or a carrier or mixtures andcombinations thereof.
 6. The method of claim 5, wherein the carriercomprising low molecular weight alcohols having between 1 and 5 carbonatoms or mixtures and combinations thereof, where one or more of thecarbon atoms may be an oxygen atom.
 7. The method of claim 1, wherein:the non amine polymerizable monomers are ethylenically unsaturatedmononers and diene monomers, the substituents of the substitutedheterocyclic aromatic amines are carbyl groups having between aboutbetween about 1 and 40 carbon atoms and the required hydrogen atoms tosatisfy the valence and where one or more of the carbon atoms can bereplaced by one or more hetero atoms selected from the group consistingof boron, nitrogen, oxygen, phosphorus, sulfur or mixture orcombinations thereof and where one or more of the hydrogen atoms can bereplaced by one or more single valence atoms selected from the groupconsisting of fluorine, chlorine, bromine, iodine or mixtures orcombinations thereof. the heterocyclic aromatic amines, substitutedheterocyclic aromatic amines comprise aniline and alkyl anilines ormixtures of alkyl anilines, pyridines and alkyl pyridines or mixtures ofalkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkylpyrroles, piperidine and alkyl piperidines or mixtures of alkylpiperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkylpyrrolidines, indole and alkyl indoles or mixture of alkyl indoles,imidazole and alkyl imidazole or mixtures of alkyl imidazole, quinolineand alkyl quinoline or mixture of alkyl quinoline, isoquinoline andalkyl isoquinoline or mixture of alkyl isoquinoline, pyrazine and alkylpyrazine or mixture of alkyl pyrazine, quinoxaline and alkyl quinoxalineor mixture of alkyl quinoxaline, acridine and alkyl acridine or mixtureof alkyl acridine, pyrimidine and alkyl pyrimidine or mixture of alkylpyrimidine, quinazoline and alkyl quinazoline or mixture of alkylquinazoline, or mixtures or combinations thereof, and the polymers andcopolymers comprise polymer and copolymers of vinyl pyridine, vinylsubstituted pyridine, vinyl pyrrole, vinyl substituted pyrroles, vinylpiperidine, vinyl substituted piperidines, vinyl pyrrolidine, vinylsubstituted pyrrolidines, vinyl indole, vinyl substituted indoles, vinylimidazole, vinyl substituted imidazole, vinyl quinoline, vinylsubstituted quinoline, vinyl isoquinoline, vinyl substitutedisoquinoline, vinyl pyrazine, vinyl substituted pyrazine, vinylquinoxaline, vinyl substituted quinoxaline, vinyl acridine, vinylsubstituted acridine, vinyl pyrimidine, vinyl substituted pyrimidine,vinyl quinazoline, vinyl substituted quinazoline, or mixtures andcombinations thereof.
 8. A method for drilling including the steps of:while drilling, circulating a first drilling fluid to provide bitlubrication, heat removal and cutting removal, upon encountering anunderground structure that produces undesirable quantities ofparticulate solids, changing the first drilling fluid to a seconddrilling fluid including an aggregating composition comprisingheterocyclic aromatic amines, substituted heterocyclic aromatic amines,poly vinyl heterocyclic aromatic amines, co-polymers of vinylheterocyclic aromatic amine and non amine polymerizable monomers, ormixtures and combinations thereof in the absence of phosphate esters andamine-phosphate reaction products to provide bit lubrication, heatremoval and cutting removal and to alter an aggregation potential or anabsolute value of a zeta potential of the particulate solids in thedrilling fluid or formation or that becomes entrained in the drillingfluid to increase solids removal and to decrease particles flowing fromthe formation into the drilling fluid.
 9. The method of claim 8, whereindrilling conditions comprise over-pressure drilling conditions,under-balanced drilling conditions, or under managed pressure drillingconditions.
 10. The method of claim 9, wherein the drilling conditionsare under-balanced drilling conditions.
 11. The method of claim 9,wherein the drilling conditions are managed pressure drillingconditions.
 12. The method of claim 8, wherein the aggregatingcomposition further comprises ethoxylated alcohols, or glymes or acarrier or mixtures and combinations thereof.
 13. The method of claim 8,further comprising the step of: after passing through the structure thatproduces an undesired quantities of particulate solids, change thesecond drilling fluid to the first drilling fluid or a third drillingfluid.
 14. A method for fracturing a formation including the step of:pumping a fracturing fluid including a proppant into a producingformation at a pressure sufficient to fracture the formation and toenhance productivity, where the proppant props open the formation afterfracturing, and where the proppant comprises a solid particles treatedwith a treating composition comprising heterocyclic aromatic amines,substituted heterocyclic aromatic amines, poly vinyl heterocyclicaromatic amines, co-polymers of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers, or mixtures and combinations thereofin the absence of phosphate esters under conditions sufficient for thecomposition to form a partial or complete coating on the particles. 15.The method of claim 14, wherein the fracturing fluid further includes anaggregating composition comprising heterocyclic aromatic amines,substituted heterocyclic aromatic amines, poly vinyl heterocyclicaromatic amines, co-polymers of vinyl heterocyclic aromatic amine andnon amine polymerizable monomers, or mixtures and combinations thereofin the absence of phosphate esters, where the aggregating compositionresults in a modification of an aggregation propensity, and/orzeta-potential of the proppant, formation particles and/or formationsurfaces so that the formation particles and/or proppant aggregateand/or cling to the formation surfaces.
 16. The method of claim 14,wherein the aggregating composition further comprises ethoxylatedalcohols, or glymes or a carrier or mixtures and combinations thereof.17. The method of claim 16, wherein the carrier comprising low molecularweight alcohols having between 1 and 5 carbon atoms or mixtures andcombinations thereof, where one or more of the carbon atoms may be anoxygen atom. The method of claim 14, wherein the non amine polymerizablemonomers are ethylenically unsaturated mononers and diene monomers, thesubstituents of the substituted heterocyclic aromatic amines are carbylgroups having between about between about 1 and 40 carbon atoms and therequired hydrogen atoms to satisfy the valence and where one or more ofthe carbon atoms can be replaced by one or more hetero atoms selectedfrom the group consisting of boron, nitrogen, oxygen, phosphorus, sulfuror mixture or combinations thereof and where one or more of the hydrogenatoms can be replaced by one or more single valence atoms selected fromthe group consisting of fluorine, chlorine, bromine, iodine or mixturesor combinations thereof. the heterocyclic aromatic amines, substitutedheterocyclic aromatic amines comprise aniline and alkyl anilines ormixtures of alkyl anilines, pyridines and alkyl pyridines or mixtures ofalkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkylpyrroles, piperidine and alkyl piperidines or mixtures of alkylpiperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkylpyrrolidines, indole and alkyl indoles or mixture of alkyl indoles,imidazole and alkyl imidazole or mixtures of alkyl imidazole, quinolineand alkyl quinoline or mixture of alkyl quinoline, isoquinoline andalkyl isoquinoline or mixture of alkyl isoquinoline, pyrazine and alkylpyrazine or mixture of alkyl pyrazine, quinoxaline and alkyl quinoxalineor mixture of alkyl quinoxaline, acridine and alkyl acridine or mixtureof alkyl acridine, pyrimidine and alkyl pyrimidine or mixture of alkylpyrimidine, quinazoline and alkyl quinazoline or mixture of alkylquinazoline, or mixtures or combinations thereof, and the polymers andcopolymers comprise polymer and copolymers of vinyl pyridine, vinylsubstituted pyridine, vinyl pyrrole, vinyl substituted pyrroles, vinylpiperidine, vinyl substituted piperidines, vinyl pyrrolidine, vinylsubstituted pyrrolidines, vinyl indole, vinyl substituted indoles, vinylimidazole, vinyl substituted imidazole, vinyl quinoline, vinylsubstituted quinoline, vinyl isoquinoline, vinyl substitutedisoquinoline, vinyl pyrazine, vinyl substituted pyrazine, vinylquinoxaline, vinyl substituted quinoxaline, vinyl acridine, vinylsubstituted acridine, vinyl pyrimidine, vinyl substituted pyrimidine,vinyl quinazoline, vinyl substituted quinazoline, or mixtures andcombinations thereof.
 18. A method for fracturing a formation includingthe step of: pumping a fracturing fluid including an aggregatingcomposition comprising heterocyclic aromatic amines, substitutedheterocyclic aromatic amines, poly vinyl heterocyclic aromatic amines,co-polymers of vinyl heterocyclic aromatic amine and non aminepolymerizable monomers, or mixtures or combinations thereof in theabsence of phosphate esters, into a producing formation at a pressuresufficient to fracture the formation and to enhance productivity, wherethe aggregating composition results in an altering an aggregationpropensity, potential and/or zeta-potential of the formation particlesand/or formation surfaces so that the formation particles aggregateand/or cling to the formation surfaces, and pumping a proppantcomprising a uncoated and/or coated particles after fracturing so thatthe particles prop open the fracture formation and where the coatedparticles tend to aggregate on the formation surfaces and/or formationparticles formed during fracturing.
 19. The method of claim 18, whereinthe aggregating composition further comprises ethoxylated alcohols, orglymes or a carrier or mixtures and combinations thereof.
 20. The methodof claim 19, wherein the carrier comprising low molecular weightalcohols having between 1 and 5 carbon atoms or mixtures andcombinations thereof, where one or more of the carbon atoms may be anoxygen atom. The method of claim 18, wherein the non amine polymerizablemonomers are ethylenically unsaturated mononers and diene monomers, thesubstituents of the substituted heterocyclic aromatic amines are carbylgroups having between about between about 1 and 40 carbon atoms and therequired hydrogen atoms to satisfy the valence and where one or more ofthe carbon atoms can be replaced by one or more hetero atoms selectedfrom the group consisting of boron, nitrogen, oxygen, phosphorus, sulfuror mixture or combinations thereof and where one or more of the hydrogenatoms can be replaced by one or more single valence atoms selected fromthe group consisting of fluorine, chlorine, bromine, iodine or mixturesor combinations thereof. the heterocyclic aromatic amines, substitutedheterocyclic aromatic amines comprise aniline and alkyl anilines ormixtures of alkyl anilines, pyridines and alkyl pyridines or mixtures ofalkyl pyridines, pyrrole and alkyl pyrroles or mixtures of alkylpyrroles, piperidine and alkyl piperidines or mixtures of alkylpiperidines, pyrrolidine and alkyl pyrrolidines or mixtures of alkylpyrrolidines, indole and alkyl indoles or mixture of alkyl indoles,imidazole and alkyl imidazole or mixtures of alkyl imidazole, quinolineand alkyl quinoline or mixture of alkyl quinoline, isoquinoline andalkyl isoquinoline or mixture of alkyl isoquinoline, pyrazine and alkylpyrazine or mixture of alkyl pyrazine, quinoxaline and alkyl quinoxalineor mixture of alkyl quinoxaline, acridine and alkyl acridine or mixtureof alkyl acridine, pyrimidine and alkyl pyrimidine or mixture of alkylpyrimidine, quinazoline and alkyl quinazoline or mixture of alkylquinazoline, or mixtures or combinations thereof, and the polymers andcopolymers comprise polymer and copolymers of vinyl pyridine, vinylsubstituted pyridine, vinyl pyrrole, vinyl substituted pyrroles, vinylpiperidine, vinyl substituted piperidines, vinyl pyrrolidine, vinylsubstituted pyrrolidines, vinyl indole, vinyl substituted indoles, vinylimidazole, vinyl substituted imidazole, vinyl quinoline, vinylsubstituted quinoline, vinyl isoquinoline, vinyl substitutedisoquinoline, vinyl pyrazine, vinyl substituted pyrazine, vinylquinoxaline, vinyl substituted quinoxaline, vinyl acridine, vinylsubstituted acridine, vinyl pyrimidine, vinyl substituted pyrimidine,vinyl quinazoline, vinyl substituted quinazoline, or mixtures andcombinations thereof.